US3227666A - Preparation of polyurethane foams containing an aluminum silicate filler - Google Patents
Preparation of polyurethane foams containing an aluminum silicate filler Download PDFInfo
- Publication number
- US3227666A US3227666A US210234A US21023462A US3227666A US 3227666 A US3227666 A US 3227666A US 210234 A US210234 A US 210234A US 21023462 A US21023462 A US 21023462A US 3227666 A US3227666 A US 3227666A
- Authority
- US
- United States
- Prior art keywords
- amine
- reactive hydrogen
- clay
- suspension
- liquid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000945 filler Substances 0.000 title claims description 14
- 238000002360 preparation method Methods 0.000 title claims description 12
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 title claims description 9
- 229920005830 Polyurethane Foam Polymers 0.000 title description 5
- 239000011496 polyurethane foam Substances 0.000 title description 5
- 239000001257 hydrogen Substances 0.000 claims description 49
- 229910052739 hydrogen Inorganic materials 0.000 claims description 49
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical class [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 48
- 239000007787 solid Substances 0.000 claims description 36
- 239000000725 suspension Substances 0.000 claims description 32
- 239000007788 liquid Substances 0.000 claims description 29
- 239000000203 mixture Substances 0.000 claims description 21
- 229920002635 polyurethane Polymers 0.000 claims description 17
- 239000004814 polyurethane Substances 0.000 claims description 17
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 14
- 239000000194 fatty acid Substances 0.000 claims description 14
- 229930195729 fatty acid Natural products 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 12
- 229920000728 polyester Polymers 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 9
- 229920001281 polyalkylene Polymers 0.000 claims description 9
- 239000004094 surface-active agent Substances 0.000 claims description 8
- 150000002170 ethers Chemical class 0.000 claims description 7
- 150000001298 alcohols Chemical class 0.000 claims description 5
- 230000001413 cellular effect Effects 0.000 claims description 5
- 239000004604 Blowing Agent Substances 0.000 claims description 4
- 150000007513 acids Chemical class 0.000 claims description 4
- 150000004665 fatty acids Chemical class 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical class [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 claims 1
- 239000006260 foam Substances 0.000 description 39
- 239000004927 clay Substances 0.000 description 36
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 28
- -1 Z-ethylhexanol- 2 Chemical compound 0.000 description 27
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical group O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 27
- 235000012211 aluminium silicate Nutrition 0.000 description 26
- 150000001412 amines Chemical class 0.000 description 25
- 239000005995 Aluminium silicate Substances 0.000 description 21
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 20
- 229910052901 montmorillonite Inorganic materials 0.000 description 19
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical group O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 16
- 239000000376 reactant Substances 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 14
- 238000009472 formulation Methods 0.000 description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 13
- 125000005442 diisocyanate group Chemical group 0.000 description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000000463 material Substances 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 11
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- 239000005416 organic matter Substances 0.000 description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- 239000002585 base Substances 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 8
- 239000003960 organic solvent Substances 0.000 description 8
- 230000020477 pH reduction Effects 0.000 description 8
- 229920005862 polyol Polymers 0.000 description 8
- 239000002245 particle Substances 0.000 description 7
- 150000003077 polyols Chemical class 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 5
- 235000012216 bentonite Nutrition 0.000 description 5
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 5
- 239000004359 castor oil Substances 0.000 description 5
- 235000019438 castor oil Nutrition 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 5
- 150000008282 halocarbons Chemical class 0.000 description 5
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 5
- HXVNBWAKAOHACI-UHFFFAOYSA-N 2,4-dimethyl-3-pentanone Chemical compound CC(C)C(=O)C(C)C HXVNBWAKAOHACI-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 239000000440 bentonite Substances 0.000 description 4
- 229910000278 bentonite Inorganic materials 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 239000012948 isocyanate Substances 0.000 description 4
- 150000002513 isocyanates Chemical class 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000003784 tall oil Substances 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 3
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid group Chemical group C(CCCCCCC\C=C/CCCCCCCC)(=O)O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 150000005846 sugar alcohols Polymers 0.000 description 3
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- HRXZRAXKKNUKRF-UHFFFAOYSA-N 4-ethylaniline Chemical compound CCC1=CC=C(N)C=C1 HRXZRAXKKNUKRF-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 239000004606 Fillers/Extenders Substances 0.000 description 2
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- NMJJFJNHVMGPGM-UHFFFAOYSA-N butyl formate Chemical compound CCCCOC=O NMJJFJNHVMGPGM-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- ILRSCQWREDREME-UHFFFAOYSA-N dodecanamide Chemical compound CCCCCCCCCCCC(N)=O ILRSCQWREDREME-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 229940102253 isopropanolamine Drugs 0.000 description 2
- 229910052622 kaolinite Inorganic materials 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 235000021388 linseed oil Nutrition 0.000 description 2
- 239000000944 linseed oil Substances 0.000 description 2
- XMYQHJDBLRZMLW-UHFFFAOYSA-N methanolamine Chemical compound NCO XMYQHJDBLRZMLW-UHFFFAOYSA-N 0.000 description 2
- 229940087646 methanolamine Drugs 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- CIXSDMKDSYXUMJ-UHFFFAOYSA-N n,n-diethylcyclohexanamine Chemical compound CCN(CC)C1CCCCC1 CIXSDMKDSYXUMJ-UHFFFAOYSA-N 0.000 description 2
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 description 2
- 229940049964 oleate Drugs 0.000 description 2
- 125000006353 oxyethylene group Chemical group 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 235000012424 soybean oil Nutrition 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 150000003606 tin compounds Chemical class 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 1
- BOSAWIQFTJIYIS-UHFFFAOYSA-N 1,1,1-trichloro-2,2,2-trifluoroethane Chemical compound FC(F)(F)C(Cl)(Cl)Cl BOSAWIQFTJIYIS-UHFFFAOYSA-N 0.000 description 1
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- OKIRBHVFJGXOIS-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC=C1C(C)C OKIRBHVFJGXOIS-UHFFFAOYSA-N 0.000 description 1
- KNKRKFALVUDBJE-UHFFFAOYSA-N 1,2-dichloropropane Chemical compound CC(Cl)CCl KNKRKFALVUDBJE-UHFFFAOYSA-N 0.000 description 1
- VGHSXKTVMPXHNG-UHFFFAOYSA-N 1,3-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC(N=C=O)=C1 VGHSXKTVMPXHNG-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 description 1
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 description 1
- HLVFKOKELQSXIQ-UHFFFAOYSA-N 1-bromo-2-methylpropane Chemical compound CC(C)CBr HLVFKOKELQSXIQ-UHFFFAOYSA-N 0.000 description 1
- SZBXTBGNJLZMHB-UHFFFAOYSA-N 1-chloro-2,4-diisocyanatobenzene Chemical compound ClC1=CC=C(N=C=O)C=C1N=C=O SZBXTBGNJLZMHB-UHFFFAOYSA-N 0.000 description 1
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 description 1
- YIOGLGOXZGOFCZ-UHFFFAOYSA-N 1-dodecyl-2h-pyridine Chemical compound CCCCCCCCCCCCN1CC=CC=C1 YIOGLGOXZGOFCZ-UHFFFAOYSA-N 0.000 description 1
- OUKZCQQNMWXMNE-UHFFFAOYSA-N 1-hexylpyrrolidine Chemical compound CCCCCCN1CCCC1 OUKZCQQNMWXMNE-UHFFFAOYSA-N 0.000 description 1
- GEZGAZKEOUKLBR-UHFFFAOYSA-N 1-phenylpyrrole Chemical compound C1=CC=CN1C1=CC=CC=C1 GEZGAZKEOUKLBR-UHFFFAOYSA-N 0.000 description 1
- KFSJCAKQTAGWBH-UHFFFAOYSA-N 2,4-dihexylphenol Chemical compound CCCCCCC1=CC=C(O)C(CCCCCC)=C1 KFSJCAKQTAGWBH-UHFFFAOYSA-N 0.000 description 1
- MGZCLRWCEUBEGO-UHFFFAOYSA-N 2-(2-propan-2-yloxyethoxy)propane Chemical compound CC(C)OCCOC(C)C MGZCLRWCEUBEGO-UHFFFAOYSA-N 0.000 description 1
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 1
- CYEJMVLDXAUOPN-UHFFFAOYSA-N 2-dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=CC=C1O CYEJMVLDXAUOPN-UHFFFAOYSA-N 0.000 description 1
- PFNHSEQQEPMLNI-UHFFFAOYSA-N 2-methyl-1-pentanol Chemical compound CCCC(C)CO PFNHSEQQEPMLNI-UHFFFAOYSA-N 0.000 description 1
- DTFKRVXLBCAIOZ-UHFFFAOYSA-N 2-methylanisole Chemical compound COC1=CC=CC=C1C DTFKRVXLBCAIOZ-UHFFFAOYSA-N 0.000 description 1
- LMRKVKPRHROQRR-UHFFFAOYSA-N 4-butylmorpholine Chemical compound CCCCN1CCOCC1 LMRKVKPRHROQRR-UHFFFAOYSA-N 0.000 description 1
- KLPPPIIIEMUEGP-UHFFFAOYSA-N 4-dodecylaniline Chemical compound CCCCCCCCCCCCC1=CC=C(N)C=C1 KLPPPIIIEMUEGP-UHFFFAOYSA-N 0.000 description 1
- HVCNXQOWACZAFN-UHFFFAOYSA-N 4-ethylmorpholine Chemical compound CCN1CCOCC1 HVCNXQOWACZAFN-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 1
- KKIVMQUXDIKPFJ-UHFFFAOYSA-N CCCCCCCCCCc1c(O)cccc1O Chemical compound CCCCCCCCCCc1c(O)cccc1O KKIVMQUXDIKPFJ-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000004338 Dichlorodifluoromethane Substances 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- LWZFANDGMFTDAV-JOCBIADPSA-N [(2r)-2-[(2r,3r,4r)-3,4-dihydroxyoxolan-2-yl]-2-hydroxyethyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@@H](O)[C@H]1O LWZFANDGMFTDAV-JOCBIADPSA-N 0.000 description 1
- ITBPIKUGMIZTJR-UHFFFAOYSA-N [bis(hydroxymethyl)amino]methanol Chemical compound OCN(CO)CO ITBPIKUGMIZTJR-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000005263 alkylenediamine group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000000732 arylene group Chemical group 0.000 description 1
- HYGWNUKOUCZBND-UHFFFAOYSA-N azanide Chemical compound [NH2-] HYGWNUKOUCZBND-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- UNYSKUBLZGJSLV-UHFFFAOYSA-L calcium;1,3,5,2,4,6$l^{2}-trioxadisilaluminane 2,4-dioxide;dihydroxide;hexahydrate Chemical compound O.O.O.O.O.O.[OH-].[OH-].[Ca+2].O=[Si]1O[Al]O[Si](=O)O1.O=[Si]1O[Al]O[Si](=O)O1 UNYSKUBLZGJSLV-UHFFFAOYSA-L 0.000 description 1
- VNSBYDPZHCQWNB-UHFFFAOYSA-N calcium;aluminum;dioxido(oxo)silane;sodium;hydrate Chemical compound O.[Na].[Al].[Ca+2].[O-][Si]([O-])=O VNSBYDPZHCQWNB-UHFFFAOYSA-N 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 229910052676 chabazite Inorganic materials 0.000 description 1
- PXKHGMGELZGJQE-ILBGXUMGSA-N chloramphenicol palmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@@H](NC(=O)C(Cl)Cl)[C@H](O)C1=CC=C([N+]([O-])=O)C=C1 PXKHGMGELZGJQE-ILBGXUMGSA-N 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- QYIQRHGZOPNRKD-UHFFFAOYSA-L di(propan-2-yl)tin(2+);diacetate Chemical compound CC([O-])=O.CC([O-])=O.CC(C)[Sn+2]C(C)C QYIQRHGZOPNRKD-UHFFFAOYSA-L 0.000 description 1
- PNOXNTGLSKTMQO-UHFFFAOYSA-L diacetyloxytin Chemical compound CC(=O)O[Sn]OC(C)=O PNOXNTGLSKTMQO-UHFFFAOYSA-L 0.000 description 1
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical compound C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 description 1
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 1
- 235000019404 dichlorodifluoromethane Nutrition 0.000 description 1
- 229910001649 dickite Inorganic materials 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 229940043237 diethanolamine Drugs 0.000 description 1
- BXVLQFGQYHYURU-UHFFFAOYSA-N diethyltin Chemical compound CC[Sn]CC BXVLQFGQYHYURU-UHFFFAOYSA-N 0.000 description 1
- DDWASQUGEVZTFH-UHFFFAOYSA-L dihexyltin(2+);octadecanoate Chemical compound CCCCCC[Sn+2]CCCCCC.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O DDWASQUGEVZTFH-UHFFFAOYSA-L 0.000 description 1
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 description 1
- 229940043276 diisopropanolamine Drugs 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- 229940035422 diphenylamine Drugs 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical group CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 229940031098 ethanolamine Drugs 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- LIWAQLJGPBVORC-UHFFFAOYSA-N ethylmethylamine Chemical compound CCNC LIWAQLJGPBVORC-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000012013 faujasite Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 1
- 229940083124 ganglion-blocking antiadrenergic secondary and tertiary amines Drugs 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 229910001683 gmelinite Inorganic materials 0.000 description 1
- 229910000271 hectorite Inorganic materials 0.000 description 1
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 description 1
- TZMQHOJDDMFGQX-UHFFFAOYSA-N hexane-1,1,1-triol Chemical compound CCCCCC(O)(O)O TZMQHOJDDMFGQX-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- QTBFPMKWQKYFLR-UHFFFAOYSA-N isobutyl chloride Chemical compound CC(C)CCl QTBFPMKWQKYFLR-UHFFFAOYSA-N 0.000 description 1
- 150000002531 isophthalic acids Chemical class 0.000 description 1
- 235000020778 linoleic acid Nutrition 0.000 description 1
- 239000006194 liquid suspension Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- YWFWDNVOPHGWMX-UHFFFAOYSA-N n,n-dimethyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)C YWFWDNVOPHGWMX-UHFFFAOYSA-N 0.000 description 1
- KUDPGZONDFORKU-UHFFFAOYSA-N n-chloroaniline Chemical compound ClNC1=CC=CC=C1 KUDPGZONDFORKU-UHFFFAOYSA-N 0.000 description 1
- MJCJUDJQDGGKOX-UHFFFAOYSA-N n-dodecyldodecan-1-amine Chemical compound CCCCCCCCCCCCNCCCCCCCCCCCC MJCJUDJQDGGKOX-UHFFFAOYSA-N 0.000 description 1
- RQAKESSLMFZVMC-UHFFFAOYSA-N n-ethenylacetamide Chemical compound CC(=O)NC=C RQAKESSLMFZVMC-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- FJDUDHYHRVPMJZ-UHFFFAOYSA-N nonan-1-amine Chemical compound CCCCCCCCCN FJDUDHYHRVPMJZ-UHFFFAOYSA-N 0.000 description 1
- FDJSESZWPWMLEC-UHFFFAOYSA-N nonane Chemical compound CCCCCCCC[CH2+] FDJSESZWPWMLEC-UHFFFAOYSA-N 0.000 description 1
- 229910000273 nontronite Inorganic materials 0.000 description 1
- BKIMMITUMNQMOS-UHFFFAOYSA-N normal nonane Natural products CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 1
- CYCFYXLDTSNTGP-UHFFFAOYSA-L octadecanoate;tin(2+) Chemical compound [Sn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CYCFYXLDTSNTGP-UHFFFAOYSA-L 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical class CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- NOUWNNABOUGTDQ-UHFFFAOYSA-N octane Chemical compound CCCCCCC[CH2+] NOUWNNABOUGTDQ-UHFFFAOYSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000003791 organic solvent mixture Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- DGTNSSLYPYDJGL-UHFFFAOYSA-N phenyl isocyanate Chemical compound O=C=NC1=CC=CC=C1 DGTNSSLYPYDJGL-UHFFFAOYSA-N 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002717 polyvinylpyridine Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910000275 saponite Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 239000001587 sorbitan monostearate Substances 0.000 description 1
- 229940035048 sorbitan monostearate Drugs 0.000 description 1
- 235000011076 sorbitan monostearate Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- KFUSEUYYWQURPO-OWOJBTEDSA-N trans-1,2-dichloroethene Chemical compound Cl\C=C\Cl KFUSEUYYWQURPO-OWOJBTEDSA-N 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- ABVVEAHYODGCLZ-UHFFFAOYSA-N tridecan-1-amine Chemical compound CCCCCCCCCCCCCN ABVVEAHYODGCLZ-UHFFFAOYSA-N 0.000 description 1
- 229940086542 triethylamine Drugs 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0066—Use of inorganic compounding ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
Definitions
- This invention relates to a method for the production of polyurethane foams having improved physical properties and to a method for incorporating inorganic fillers and extenders into urethane foams to obtain said improved properties.
- Foamed or cellular polyurethanes have been prepared with a wide variety of physical properties ranging from rigid insulating materials to soft flexible cushioning materials. These materials are prepared by reacting a liquid having a reactive hydrogen, e.g., polyester or polyalkylene ether with an organic diisocyanate in the presence of a gas generating reactant.
- a liquid having a reactive hydrogen e.g., polyester or polyalkylene ether
- an organic diisocyanate e.g., a reactive hydrogen
- the cost of the raw materials is relatively high, although attempts have been made to substitute relatively inexpensive fatty acid glycerides, e.g., castor oil, tall oil, etc., for the reactive hydrogen liquid and to increase the volume of the product by increasing the foaming during reaction.
- the dispersion of filler material in the polymeric reactant is highly stable and can be stored for prolonger periods without settling. Consequently, the foam formulation is greatly simplified since the solid filler can be dispersed into the reactive hydrogen liquid component prior to its reaction with the organic diisocyanate.
- any organic solvent of greater volatility than the reactive hydrogen liquid can be used for the dispersing medium, i.e., with an initial atmospheric boiling point below about 200 C., and preferably below C.
- hydrocarbons i.e., with an initial atmospheric boiling point below about 200 C., and preferably below C.
- suitable hydrocarbons are the aliphatic series such as n-pentane, isopentane, hexane, isohexane, heptane, octane, isooctane, nonane, decane, etc.
- Aromatic solvents can be used such as benzene, toluene, xylenes, ethylbenzene, cumene, diisopropylbenzene, etc.
- Halogenated hydrocarbons which can be used include the following: ethyl chloride, ethyl bromide, methylene chloride, ethylidene dichloride, acetylene dichloride, chloroform, isobutyl chloride, trichloroethane, carbon tetrachloride, n-butyl chloride, ethylene chloride, isobutyl bromide, 1,2-dichloropropane, isoarnyl chloride, chlorobenzene, bromo'benzene, dichlorobenzene, chloroaniline, etc.
- Alcohols can also be used such as methanol, ethanol, isopropanol, butanol, isoamyl alcohol, 2-methylpentanol-1, Z-ethylhexanol- 2, furfural alcohol, etc.
- Ketones are useful such as acetone, methyl ethyl ketone, diethyl ketone, methyl butyl ketone, diisopropyl ketone, diisobutyl ketone, etc.
- oxygenated solvents e.g., ethers, and esters
- ethers e.g., ethers, and esters
- diethyl ether e.g., ethers, and esters
- diisopropyl ether ethyl acetate, methyl ethyl ketone, propyl formate, ethyl propionate, diethyl ketone, butyl formate, methyl isobutyl ketone, ethyl butyrate, diisopropyl ketone, arnyl acetate, ethylene glycol diisopropyl ether, ethyl, benzyl ether, methyl o-tolyl ether, etc.
- diethyl ether ethyl fol-mate
- ethyl acetate diisopropyl ether
- ethyl acetate methyl ethyl ketone
- propyl formate
- the filler solids employed in my invention are ion exchange solids and comprise the synthetic and naturally occurring aluminum silicates and organophilic aluminum silicates obtained therefrom.
- zeolitic materials are the following: chabazite, analcite, gmelinite, faujasite, molecular sieves, etc.
- the preferred aluminum silicates are the naturally occurring clays which are available in a wide variety of chemical and physical properties. For the purposes of my invention, these clays can be classified into the kaolinite group and the montmorillonite groups.
- the kaolinite group comprises hydrous aluminum silicates which are the chief constituents of the white clay kaolin. Included in this group are the following: anauxite, collyrite, dickite, ferrikaolinite, kaolin, kaolinite, metakaolinite, metanacrite, microvermiculite, nacrite, neokaolin, severite, etc. These aluminum silicate in general have a low base exchange capacity, generally less than about 20 milliequivalents per hundred grams. They have a non-expanding crystalline lattice and generally conform to the kaolinite structure of an
- the montmorillonite group includes the complex clays having 3-layer crystal lattices which swell or expand in solvents. Included in this group are the following: amar- 3 gosite, beidellite, bentonite, chloropal, erinite, ferromontmorillonite, hectorite, metabentonite, montmorillonite,
- nontronite, otaylite, saponite, etc. These clays are commonly found in admixture in bentonite clays having an average aluminum oxide content less than about 20 percent.
- the bentonite clays also have a high base exchange capacity, commonly between about 80 and 150 milliequivalents per 100 grams of air dried clay.
- These swelling or expanding lattice montmorillonite clays are found in Wyoming, South Dakota, Montana, Utah, Nevada and California.
- the aforedescribed clays and natural zeolites are usually found in a form wherein the base exchange sites are occupied with alkali and/or alkaline earth metals such as sodium, calcium and magnesium.
- the commercial synthetic zeolites are also available with their exchange sites occupied by an alkali metal or alkaline earth metal.
- the clays and zeolites can be base exchanged to prepare aluminum silicates which have various other cations at the base exchange sites such as the cations of the metals of Groups I through VIII of the Periodic Table, ammonium and quaternary ammonium organic cations, the latter comprising organophilic clays.
- the member of the montmorillonite group will form improved polyurethane foams only if organophilic derivatives are employed.
- be tween about 2 and 50 weight percent clay based solids can be incorporated into the urethane foam; preferably between about and Weight percent of the organic components comprises a clay based additive.
- the organophilic derivatives of the aforementioned aluminum silicates solids are preferably prepared by acidification of the solid with a mineral acid-organic solvent mixture and reaction of the acidified solid with an organic amine. If desired, several stages of Washing and filtration can be used to free the acidified solid of salts prior to reaction with the amine.
- the mineral acid e.g., sulfuric, nitric, hydrochloric, etc., is used at a strength between about 10 and 90 percent in about 0.01 to about 4 volume ratios of acid to organic solvent.
- a sufficient amount of the acid-organic solvent is employed to obtain from 1 to about 10 times the stoichiometric amount of acid necessary to form the hydrogen clay, i.e., from 1 to about 10 times the base exchange capacity of the clay.
- the acidification is preferably conducted at ambient temperatures'and the solid recovered by filtration and thereafter washed several times with about 0.5 to 10 part of fresh solvent per part by weight of clay.
- Solvents which are employed in the acidification of the solid are preferably those in which alkali and alkaline earth metal salts of the treating acid are soluble in amounts greater than about 0.1 weight percent.
- these solvents are oxygenated organic liquids and, preferably, are the monoand polyhydric alcohols of the C -C aliphatic hydrocarbons, e.g., methanol, ethanol, ethylene glycol, isopropanol, butanol, isopentanol, etc.
- the preferred treating medium comprises hydrochloric acid in methanol.
- the acidified clay which has been acidified and washed sufiiciently to reduce its exchangable ion and soluble salt content is thereafter reacted with an organic amine to form the desired organophilic solid.
- the resultant organophilic solid remains dispersed in the organic solvent after reaction and, as such, can be added directly to the reactive hydrogen polyurethane reactant.
- the solvent e.g., methanol, is thereafter evaporated to form the stable dispersion of organophilic solid which is used in the urethane formulation.
- organophilic kaolins preferably organophilic montmorillonites are prepared by reacting the hydrogen clay suspension with an organic amine.
- this reaction is performed in the organic solvent prior to its addition to the polyurethane reactant; however the reaction with an amine can if desired be performed with the urethane reactant dispersion or organic solvent dispersion.
- organophilic kaolins can be obtained in this manner which have from 0.05 to about 10 weight percent chemically bonded organic matter, i.e., unextractible organic matter and organophilic montmorillonites can be prepared having from about 2 to weight percent chemically bonded organic matter.
- Various amines can be reacted with the acidified solid to form an organophilic solid such as the primary, secondary and tertiary amines of alkyl, alkanol, aryl, alkaryl, aralkyl, radicals having up to about 30 carbons.
- amines examples include methyl amine, methanol amine, N-methyl ethyl amine, trimethanol amine, diethanol amine, pyridine, aniline, triethyl amine, N-methanol diisopropanol amine, p-ethyl aniline, Z-methylhexanol-Z-amine, nonyl amine, N-phenyl pyrrole, dipentanol amine, diphenyl amine, N- hexyl pyrrolidine, tributyl amine, N-methyl dihexanol amine, N,N-dimethyl lauryl amine, oleyl amine, N,N'- dihexyl iminazole, recinoleyl amine, 2-phenyl lauryl amine, stearylamine, p-lauryl aniline, N-butyl ricinoleyl amine, N-lauryl pyridine, 2,6-diphenyl lauryl
- Polymeric amines and polyamines can also be employed such as the amine terminated vinyl polymers obtained by amide ion initiated polymerization of monomers such as acrylonitrile, styrene, methacrylonitrile, vinyl acetate, etc.
- amine terminated polymers having molecular weights between about 1000 and 200,000 units can be obtained by sodamide initiated polymerization and copolymerization of the aforementioned monomers in liquid ammonia at temperatures between about and about C.
- the reaction of these polymeric amines with hydrogen clays provides organophilic clays which comprise from 1 to 70 weight percent unextractible organic matter.
- polymers and copolymers examples include: polyvinylpyridine, polyvinylpyrrolidone, copolymer of styrene and vinyl pyridine, copolymer of vinyl chloride and vinyl pyridine, poly(N-vinyl acetamide), poly(N-vinylbenzarnide), copolymer of styrene and N-vinylformamide, etc.
- Amine terminated polyalkylene ethers comprise a preferred class of organic amines because they present reactive hydrogens for bonding to the polyurethane through reaction with the organic diisocyanate.
- These materials are prepared by condensation of alkylene oxides, e.g., ethylene oxide, propylene oxide with alkanol amines such as methanol amine, ethanol amine, isopropanol amine, etc.
- alkylene oxides e.g., ethylene oxide, propylene oxide
- alkanol amines such as methanol amine, ethanol amine, isopropanol amine, etc.
- condensates are available having a wide range of molecular Weights from about 70 to 15,000 units. Preferably, condensates having molecular weights between about 70 and about 1000 units are used.
- An example of a commercially available material is H-163 marketed by Union Carbide which has four ethylene oxide units condensed with isopropanol amine and a molecular weight of 163.
- polyurethane foams are well established art to which my invention is directly applicable.
- the foam is formed by reacting a reactive hydrogen liquid with an organic diisocyanate in the presence of a reactant which generates a gas.
- a catalyst is employed to obtain the proper rate of reaction and various surface active agents are added to stabilize the foam.
- the physical properties of the foamed product depend largely on the nature of the reactive hydrogen component.
- polyesters, polyalkylene ethers or fatty acid glycerides are commonly used for this reactant. Suitable materials have molecular weights between about 500 and 5000; preferably between about 1000 and 3000.
- the polyethers are essentially linear with terminal hydroxyl groups.
- the polyesters employed are prepared with excess glycol and accordingly have low acid numbers and moderate to high hydroxyl numbers.
- the reactive hydrogen liquids have hydroxyl numbers between about 300 and about 20 and acid numbers (polyesters and fatty acid glycerides) less than about 10. The hydroxyl number is a direct measure of the density of reactive hydrogens and indicates the degree of cross-linking in the product.
- rigid foams are highly cross-linked and are prepared from components having hydroxyl numbers between about 180 and about 300.
- the flexible foams are obtained from components having hydroxyl numbers between about 20 and about 100, while semi-rigid foams are obtained from components having hydroxyl numbers between about 100 and 180.
- polyesters which can be employed in the foam formulation are obtained by the reaction of saturated alkyl or aryl dibasic acids or anhydrides with polyhydric alcohols in the manner well known to the art.
- Commercially available materials are prepared from adipic, sebacic, maleic, terephthalic, isophthalic acids and ethylene glycol, trimethylol ethane, trimethylol propane, etc.
- the polyalkylene ethers useful as the reactive hydrogen liquid are obtained by polymerization of various alkylene oxides, commonly ethylene oxide or propylene oxide. Examples of such materials are mixed polyglycols of ethylene, propylene, polytetiamethylene glycol, polypropylene glycol, polyethylene glycol, etc.
- Fatty acid glycerides can also be used as the reactive hydrogen liquid to yield a low cost foam.
- Commonly employed glycerides are castor oil, tall oil, soya oil, linseed oil, etc., which are usually admixed with up to equal amounts of low molecular weight polyols to increase the density of cross-linking sites.
- low molecular weight polyols so used are triisopropanol, hexitols, ethylene glycol, trimethylol ethane, and polyhydric derivatives of alkylene diamines, e.g., Quadrol marketed by the Wyandotte Chemical Company which is N,N,N',N-tetrakis(2 hydroxypropyl) ethylene diamine.
- the diisocyanates employed in the urethane foam preparation are, in general, arylene diisocyanates and include the following: 2,4-tolylene diisocyanate, 2,6- tolylene diisocyanate, 3,3-bitolylene diisocyanate, diphenylmethane, 4,4 diisocyanate, 3,3 dimethyl diphenylrnethane, 4,4'-diisocyanate, m-phenylene diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-sulfonylbis- (phenyl isocyanate), 1 chloro-2,4-phenylene diisocyanate, l,5-tetrahydronaphthylenediisocyanate, etc.
- the amount of isocyanate employed in the formulation depends on the number of reactive hydrogens in the polyalkylene ether, polyester or fatty acid glyceride, which as previously mentioned is selected to obtain the desired degree of crosslinking.
- the amount of isocyanate employed is also determined by the nature of the gas generating agent and the density desired in the foamed product since the use of water as a gas generating agent consumes a stoichiometric amount of isocyanate.
- the diisocyanate when water is added to react with the diisocyanate, approximately 1 to about 10 equivalents of isocyanate; preferably between about 2 and about 6; are employed per equivalent of reactive hydrogen in the formulation. Substantially all the diisocyanate in excess of the equivalent amount consumed by the urethane formation is consumed in carbon dioxide formation with water.
- urethane reactants between about 1 and about 10 parts by weight of water are used per parts by weight of urethane reactants; preferably this amount is between about 2 to 7 parts per 100 parts.
- diisocyanate in excess of the stoichiometric amount needed for the reactive hydrogen liquid must be used with this technique to react with the water and liberate carbon dioxide; preferably the diisocyanate is also used in a slight excess than the additional amount consumed by reaction with water.
- a latent gas generating component such as the halogenated hydrocarbons, e.g., tn'chlorofiuormethane, trichlorotrifluoroethane, dichlorodifluoromethane, etc.
- these volatile liquids are used in amounts up to 25 weight percent of the urethane reactants, de pending on desired foam density and on character of ingredient as well as ambient conditions.
- non-ionic surface active agents can be used in amounts between about 0.5 and 5.0 weight percent of the reactants.
- silicone emulsifiers can also be used, particularly with the aforementioned halogenated hydrocarbon blowing agents.
- suitable non-ionic surface active agents are ethylene oxide condensates of vegetable oils, alcohols, phenols, organic acids and hydroxy esters. Included in such compounds are castor oil, tall oil, linseed oil condensates of ethylene oxide having 5 to 70 weight percent of oxyethylene units.
- Alkylphenol polyoxyethylene compounds having one or more alkyl side chains with about 5 to 20 carbons and 5 to 70 weight percent of an oxyethylene chain can be used, e.g., ethylene oxide condensate of lauryl phenol, of 2,4-dihexyl phenol, ,of heptenyl cresol, of decyl resorcinol, of decenyl xylenol, etc.
- Ethylene oxide condensates of fatty acids having about 10 to about 25 carbons and about 5 to 70 weight percent of ethylene oxide units are also useful, e.g., condensates with lauric, stearic, oleic, linoleic, palrnitic acids, etc.
- Ethylene oxide condensates of esterified polyhydric alcohols can also be used such as condensates of sorbitan monostearate, mannitan monolaurate, etc. having 5 to 70 weight percent of ethylene oxide units.
- the condensates at 5 to 70 weight percent ethylene oxide and fatty amines or amides with about 10 and 25 carbons can also be used such as the condensates of dodecanamide, tridecyl amine, hexadecyl amine, hetadecanamide, etc.
- Tertiary amines and/ or organic tin compounds can be used as catalysts for the reaction in the manner known to those skilled in the art.
- amine catalysts are: triethylenediamine, N-alkylmorpholines, e.g., N-methylmorpholine, N-ethylmorpholine, N-butylmorpholine, trialkyl amines, e.g., trimethylamine, dibutyl ethylarnine, dihexyl decylarnine, etc.
- tin compounds examples include tin salts of fatty acids, e.g., stannous octoate, stannous acetate, stannous propionate, stannous stearate, stannous oleate, etc.
- Dialkyl tin salts can also be used, e.g., dibutyl tin dilaurate, diethyl tin oleate, diisopropyl tin acetate, dihexyl tin stearate, etc.
- the catalyst is employed in amounts between about 1 and about 12 weight percent of the urethane reactants; preferably in amounts between about 1 and 5 weight percent.
- the ion exchange solid is dispersed in the volatile organic solvent by adding the solid to the solvent with agitation.
- the grit and large solid particles which settle from the suspension are discarded and, preferably, the suspension is elutriated to reject all particles coarser than microns and save for use all particles finer than 5 microns.
- the clarified and elutriated suspension is then ready for use in the polyurethane formulation, for acidification and/or base exchange with a quaternary organic ammonium cation prior to its use in the polyurethane formulation.
- the suspension of kaolin, organophilic kaolin or organophilic montmorillonite is added, preferably with stirring, to the liquid reactive hydrogen component of the polyurethane reactant, i.e., the polyalkylene ether, polyester or fatty acid glyceride.
- the admixture is heated under atmospheric or reduced pressures to evaporate the solvent. Generally temperatures from about 80 to about 250 C. are sufficient for this purpose. This solvent can be condensed and reused to prepare new solid suspensions.
- the solidreactive hydrogen liquid suspension so prepared is very stable, samples exhibiting little or no phase separation after storage for several weeks to several months.
- the remainder of the polyurethane preparation follows conventional practice.
- the one-shot technique is preferred, wherein the blowing agent (water or halogenated hydrocarbon), catalyst, and surfactant are added to the reactive hydrogen component and the resultant single blend is subsequently admixed with the organic diisocyanate to form a reacting mass which is discharged into the mold.
- My invention can also be used in the prepolymer technique wherein the diisocyanate is aged with all or a portion of the reactive hydrogen component for several minutes to several hours prior to addition of the catalyst.
- the reactive hydrogen component comprises the aforedescribed solid suspension of clay or organophilic clay in reactive hydrogen reactant.
- FORMULATION 1.-LOW DENSITY RIGID A crude mixture of rosin, oleic, linoleic and stearic acids in which is suspended parts by weight of an organophilic montmorillonite per 100 parts of tall oil.
- EXAMPLE 1 Samples of a commercially obtainable montmorillonite, Wyoming bentonite, and kaolinite were stirred into methanol to form suspensions of about 100 grams of clay per liter of methanol. Grit and large particles of clay settled from the suspension and removed. The degritted clay suspensions were thereafter divided into several portions and one portion of each clay suspension was used directly in the urethane foam preparation.
- each clay suspension was passed upwardly through an eleutriation zone to recover the finest portion having a particle size distribution between 0.01 and about 5 microns.
- the eleutriated fraction was again divided and one portion thereof was acidified by the addition of 10 milliliters of 38 percent hydrochloric acid per 100 grams of clay.
- the acidified clay was filtered from suspension and washed several times with 250 mililiters of methanol per 100 grams of clay, filtering the clay after each wash step.
- Each of the final suspensions of about 25 weight percent clay in methanol was thereafter divided into two fractions and an amino polyol, dioxyethylene propanol amine, was added to one fraction of each clay suspension in a suificient quantity to achieve neutralization of the hydrogen clay.
- the resultant organo montmorillonite contained about 7.5 weight percent unextractable organic matter and the resultant organokaolinite contained about 0.4 weight percent unextracta'ble organic matter.
- lonite obtained in a organic amines in amounts sufficient to neutralize the hydrogen clays.
- the resultant organoclay suspensions were then spray dried to obtain a powdered solid which was added to the polyol system.
- organoclays invest Table 1 suspension of the degritted kaol drogen sults so obtained.
- Table 2 t ine mple was ob- EXAMPLE 2 illustrates the results ob id directly to the polyol d by the prior art.
- olyol Were 3 milliliters of water, 1.5 .5 grams of dibutyl tin The polyol suspension was thereigh speed stirrer and, milled in a ball mill or heated prior to The amounts of yed are set forth ich summarizes the results.
- olyol and diisocyanate emplo g table wh The degritted kaolin emp tained by suspending kao of a urethane as heretofore practice Alsoadded to the p "grams of a silicon surfactant and 1 dilaurate catalyst.
- Clay filled foams having tensile and tear strengths greater than unfilled foams
- Samples 7 through 10 illustrate the results obtainable with organokaolin clays, which substantially duplicate the results of the inorganic kaolin filled clays, samples 1 through 6.
- Samples 11 through 14 illustrate the failure of urethane foams which occurs when inorganic montmorillonite clays are used as fillers. I have found that this behavior can be avoided by 'base exchanging an organic amine onto the clay in an amount greater than about one weight percent and the samples 14 through 21 demonstrate results obtainable with such organophilic montmorillonites. From this data it can be seen that foams of reduced density can be obtained with substantially no reduction in tensile strength compared to the unfilled foam.
- a reactive hydrogen liquid having a molecular weight between about 500 and 3,000, a hydroxyl number between about and about 300 and selected from the class consisting of polyalkylene ethers, fatty acid glycerides, polyesters of dibasic acids and dihydric alcohols having acid numbers less than about 10, and mixtures thereof, is reacted with an excess of an arylene diisocyauate in the presence of a blowing agent, a catalyst and a surface active agent; the improved method of incorporating an aluminum silicate solid filler within said cellular polyurethane which comprises forming a suspension of said aluminum silicate solid in a volatile organic liquid having a boiling point lower than said reactive hydrogen liquid, admixing said suspension with said reactive hydrogen liquid, removing said volatile organic liquid by evaporation and thereafter admixing and reacting said reactive hydrogen liquid with said arylene diisocyanate.
- said aluminum silicate solid is a clay selected from the class consisting of kaolin, orgnophilic kaolin and organophilic montmorillonitc.
- said aluminum silicate is an organophilic kaolin and is prepared by (1) suspending kaolin in an acidification medium comprising a mixture of hydrochloric acid in methanol to convert the kaolin to hydrogen kaolin, (2) filtering the resultant hydrogen kaolin from the acidification medium, (3) suspension of the filtered hydrogen kaolin solid in said volatile organic liquid,'and (4) addition of an organic amine to the suspension of said hydrogen kaolin in an amount sufficient to neutralize said hydrogen kaolin and form said organophilic kaolin having between about 0.05 and 10 weight percent of chemically bonded organic matter.
- aluminum silicate is an organomontmorillonite and is prepared by (1) suspending montmorillonite in an acidification medium comprising a mixture of hydrochloric acid in methanol to convert said montmorillonite to hydrogen montmorillonite, (2) filtering said hydrogen montmorillonite'from said acidification medium, (3) suspension of the filtered hydrogen montmorilionite solid in said volatile organic liquid, and (4) addition of an organic amine to the suspension of said hydrogen montmorillonite in an amount suflicient to neutralize said hydrogen montmorillonite and form said organophilic montmorillonite having 'between about 2 and about weight percent of chemically bonded organic matter.
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Description
United States fiatent C 3 227 666 PREPARATION onPoiYURETnANE FOAMS CONTAINING AN ALUNHNUM SILICATE FTLLER William E. Showalter, Seal Beach, Calif., assignor to Union Gil Company of California, Los Angeles, Calif., a corporation of California No Drawing. Filed July 16, 1962, Ser. No. 210,234 5 Claims. (Cl. 260-25) This invention relates to a method for the production of polyurethane foams having improved physical properties and to a method for incorporating inorganic fillers and extenders into urethane foams to obtain said improved properties.
Foamed or cellular polyurethanes have been prepared with a wide variety of physical properties ranging from rigid insulating materials to soft flexible cushioning materials. These materials are prepared by reacting a liquid having a reactive hydrogen, e.g., polyester or polyalkylene ether with an organic diisocyanate in the presence of a gas generating reactant. The cost of the raw materials is relatively high, although attempts have been made to substitute relatively inexpensive fatty acid glycerides, e.g., castor oil, tall oil, etc., for the reactive hydrogen liquid and to increase the volume of the product by increasing the foaming during reaction.
While these attempts have substantially reduced the cost of urethane foams, it is nevertheless desirable to incorporate inexpensive fillers or extenders into the foams to further reduce the cost of the expensive organic components. Among such materials are the relatively abundant clays and alumino silicates, e.g., kaolins, bentonites, zeolites, synthetic alumino silicates, etc. Previous investigators have incorporated various materials, e.g., organomontmorillonites, kaolins and organo-kaolins of a specified size range into polyurethane foams and have contended that the presence of the organo-montmorillonites tends to stabilize the foam preparation and that the kaolins of a specified size range serve to extend the foam.
I have also attempted to extend the volume of foam obtained from the polyurethane reaction by the addition of various fillers, e.g., organo montmorillonites, kaolinites, etc., directly to the polyurethane reactants. In all instances, the physical properties, such as tensile and tear strengths, of the foamed urethane were impaired by the addition of the filler. Microscopic investigation of the urethane foam products indicated that although finely divided solids were employed as fillers, these materials did not disperse into the foam but existed as solid agglomerates within the foam.
1 have now discovered that very stable suspension of solids in the reactive hydrogen liquid can be obtained when the finely divided solid fillers are first added to a volatile organic solvent to form a dispersion which is added to the reactive hydrogen liquid, i.e., polyester, polyalkylene ether or fatty acid glyceride, and the solvent thereafter evaporated. When these solid suspensions are used in the polyurethane formulation, foams of increased volume and improved physical properties are obtained. It is believed that the prior dispersion of the filler solids in an organic medium tends to defiocculate the solids and imparts an organophilic surface to the particles, permitting the polymeric reactant to wet the particles and thus form a complete and stable dispersion. The dispersion of filler material in the polymeric reactant is highly stable and can be stored for prolonger periods without settling. Consequently, the foam formulation is greatly simplified since the solid filler can be dispersed into the reactive hydrogen liquid component prior to its reaction with the organic diisocyanate.
In general, any organic solvent of greater volatility than the reactive hydrogen liquid can be used for the dispersing medium, i.e., with an initial atmospheric boiling point below about 200 C., and preferably below C. In cluded in such solvents are hydrocarbons, halogenated hydrocarbons, alcohols, ketones, ethers and esters. Exam ples of suitable hydrocarbons are the aliphatic series such as n-pentane, isopentane, hexane, isohexane, heptane, octane, isooctane, nonane, decane, etc. Aromatic solvents can be used such as benzene, toluene, xylenes, ethylbenzene, cumene, diisopropylbenzene, etc. Halogenated hydrocarbons which can be used include the following: ethyl chloride, ethyl bromide, methylene chloride, ethylidene dichloride, acetylene dichloride, chloroform, isobutyl chloride, trichloroethane, carbon tetrachloride, n-butyl chloride, ethylene chloride, isobutyl bromide, 1,2-dichloropropane, isoarnyl chloride, chlorobenzene, bromo'benzene, dichlorobenzene, chloroaniline, etc. Alcohols can also be used such as methanol, ethanol, isopropanol, butanol, isoamyl alcohol, 2-methylpentanol-1, Z-ethylhexanol- 2, furfural alcohol, etc. Ketones are useful such as acetone, methyl ethyl ketone, diethyl ketone, methyl butyl ketone, diisopropyl ketone, diisobutyl ketone, etc. Various other oxygenated solvents, e.g., ethers, and esters can also be employed such as diethyl ether, ethyl fol-mate, ethyl acetate, diisopropyl ether, ethyl acetate, methyl ethyl ketone, propyl formate, ethyl propionate, diethyl ketone, butyl formate, methyl isobutyl ketone, ethyl butyrate, diisopropyl ketone, arnyl acetate, ethylene glycol diisopropyl ether, ethyl, benzyl ether, methyl o-tolyl ether, etc.
The filler solids employed in my invention are ion exchange solids and comprise the synthetic and naturally occurring aluminum silicates and organophilic aluminum silicates obtained therefrom. Of the zeolitic materials are the following: chabazite, analcite, gmelinite, faujasite, molecular sieves, etc.
The preferred aluminum silicates are the naturally occurring clays which are available in a wide variety of chemical and physical properties. For the purposes of my invention, these clays can be classified into the kaolinite group and the montmorillonite groups.
The kaolinite group comprises hydrous aluminum silicates which are the chief constituents of the white clay kaolin. Included in this group are the following: anauxite, collyrite, dickite, ferrikaolinite, kaolin, kaolinite, metakaolinite, metanacrite, microvermiculite, nacrite, neokaolin, severite, etc. These aluminum silicate in general have a low base exchange capacity, generally less than about 20 milliequivalents per hundred grams. They have a non-expanding crystalline lattice and generally conform to the kaolinite structure of an The montmorillonite group includes the complex clays having 3-layer crystal lattices which swell or expand in solvents. Included in this group are the following: amar- 3 gosite, beidellite, bentonite, chloropal, erinite, ferromontmorillonite, hectorite, metabentonite, montmorillonite,
nontronite, otaylite, saponite, etc. These clays are commonly found in admixture in bentonite clays having an average aluminum oxide content less than about 20 percent. The bentonite clays also have a high base exchange capacity, commonly between about 80 and 150 milliequivalents per 100 grams of air dried clay. These swelling or expanding lattice montmorillonite clays are found in Wyoming, South Dakota, Montana, Utah, Nevada and California.
The aforedescribed clays and natural zeolites are usually found in a form wherein the base exchange sites are occupied with alkali and/or alkaline earth metals such as sodium, calcium and magnesium. The commercial synthetic zeolites are also available with their exchange sites occupied by an alkali metal or alkaline earth metal. The clays and zeolites can be base exchanged to prepare aluminum silicates which have various other cations at the base exchange sites such as the cations of the metals of Groups I through VIII of the Periodic Table, ammonium and quaternary ammonium organic cations, the latter comprising organophilic clays.
While I have discovered that the members of the kaolinite group can be employed in the urethane preparation with their exchange sites ocupied by any of the aforementioned cations, the member of the montmorillonite group will form improved polyurethane foams only if organophilic derivatives are employed. In general, be tween about 2 and 50 weight percent clay based solids can be incorporated into the urethane foam; preferably between about and Weight percent of the organic components comprises a clay based additive.
The organophilic derivatives of the aforementioned aluminum silicates solids are preferably prepared by acidification of the solid with a mineral acid-organic solvent mixture and reaction of the acidified solid with an organic amine. If desired, several stages of Washing and filtration can be used to free the acidified solid of salts prior to reaction with the amine. The mineral acid, e.g., sulfuric, nitric, hydrochloric, etc., is used at a strength between about 10 and 90 percent in about 0.01 to about 4 volume ratios of acid to organic solvent. A sufficient amount of the acid-organic solvent is employed to obtain from 1 to about 10 times the stoichiometric amount of acid necessary to form the hydrogen clay, i.e., from 1 to about 10 times the base exchange capacity of the clay. In general between about 0.1 and 0.5 part of clay can be treated per part by Weight of acid-solvent mixture. The acidification is preferably conducted at ambient temperatures'and the solid recovered by filtration and thereafter washed several times with about 0.5 to 10 part of fresh solvent per part by weight of clay.
Solvents which are employed in the acidification of the solid are preferably those in which alkali and alkaline earth metal salts of the treating acid are soluble in amounts greater than about 0.1 weight percent. In general, these solvents are oxygenated organic liquids and, preferably, are the monoand polyhydric alcohols of the C -C aliphatic hydrocarbons, e.g., methanol, ethanol, ethylene glycol, isopropanol, butanol, isopentanol, etc. The preferred treating medium comprises hydrochloric acid in methanol.
The acidified clay which has been acidified and washed sufiiciently to reduce its exchangable ion and soluble salt content is thereafter reacted with an organic amine to form the desired organophilic solid. The resultant organophilic solid remains dispersed in the organic solvent after reaction and, as such, can be added directly to the reactive hydrogen polyurethane reactant. The solvent e.g., methanol, is thereafter evaporated to form the stable dispersion of organophilic solid which is used in the urethane formulation.
While the aforedescribed dispersion of the hydrogen form of kaolin clays can be used in the urethane preparation, preferably organophilic kaolins, and, of necessity, organophilic montmorillonites are prepared by reacting the hydrogen clay suspension with an organic amine. Preferably this reaction is performed in the organic solvent prior to its addition to the polyurethane reactant; however the reaction with an amine can if desired be performed with the urethane reactant dispersion or organic solvent dispersion. In general, organophilic kaolins can be obtained in this manner which have from 0.05 to about 10 weight percent chemically bonded organic matter, i.e., unextractible organic matter and organophilic montmorillonites can be prepared having from about 2 to weight percent chemically bonded organic matter.
Various amines can be reacted with the acidified solid to form an organophilic solid such as the primary, secondary and tertiary amines of alkyl, alkanol, aryl, alkaryl, aralkyl, radicals having up to about 30 carbons. Examples of such amines are methyl amine, methanol amine, N-methyl ethyl amine, trimethanol amine, diethanol amine, pyridine, aniline, triethyl amine, N-methanol diisopropanol amine, p-ethyl aniline, Z-methylhexanol-Z-amine, nonyl amine, N-phenyl pyrrole, dipentanol amine, diphenyl amine, N- hexyl pyrrolidine, tributyl amine, N-methyl dihexanol amine, N,N-dimethyl lauryl amine, oleyl amine, N,N'- dihexyl iminazole, recinoleyl amine, 2-phenyl lauryl amine, stearylamine, p-lauryl aniline, N-butyl ricinoleyl amine, N-lauryl pyridine, 2,6-diphenyl lauryl amine, dilauryl amine, diricinoleyl amine, etc. In general, organophilic clays so obtained comprise between about 0.05 and 15 weight percent of unextractible organic matter.
Polymeric amines and polyamines can also be employed such as the amine terminated vinyl polymers obtained by amide ion initiated polymerization of monomers such as acrylonitrile, styrene, methacrylonitrile, vinyl acetate, etc. In general, amine terminated polymers having molecular weights between about 1000 and 200,000 units can be obtained by sodamide initiated polymerization and copolymerization of the aforementioned monomers in liquid ammonia at temperatures between about and about C. The reaction of these polymeric amines with hydrogen clays provides organophilic clays which comprise from 1 to 70 weight percent unextractible organic matter.
Polymeric polyamines obtained by the polymerization of N-vinyl amines and vinyl substituted heterocyclic nitrogen compounds such as vinyl pyridine, N-vinyl acetamide, N-vinylbenzami-de, N-vinyl formamide, etc. or copolymerization of these amino monomers with other vinyl monomers such as styrene, vinyl acetates, vinyl chloride, acrylonitrile, methacrylonitrile, etc., can also be used. Examples of such polymers and copolymers are: polyvinylpyridine, polyvinylpyrrolidone, copolymer of styrene and vinyl pyridine, copolymer of vinyl chloride and vinyl pyridine, poly(N-vinyl acetamide), poly(N-vinylbenzarnide), copolymer of styrene and N-vinylformamide, etc. Amine terminated polyalkylene ethers comprise a preferred class of organic amines because they present reactive hydrogens for bonding to the polyurethane through reaction with the organic diisocyanate. These materials are prepared by condensation of alkylene oxides, e.g., ethylene oxide, propylene oxide with alkanol amines such as methanol amine, ethanol amine, isopropanol amine, etc. These condensates are available having a wide range of molecular Weights from about 70 to 15,000 units. Preferably, condensates having molecular weights between about 70 and about 1000 units are used. An example of a commercially available material is H-163 marketed by Union Carbide which has four ethylene oxide units condensed with isopropanol amine and a molecular weight of 163.
The formulation of polyurethane foams is a well established art to which my invention is directly applicable. In general, the foam is formed by reacting a reactive hydrogen liquid with an organic diisocyanate in the presence of a reactant which generates a gas. A catalyst is employed to obtain the proper rate of reaction and various surface active agents are added to stabilize the foam.
The physical properties of the foamed product depend largely on the nature of the reactive hydrogen component. As previously mentioned, polyesters, polyalkylene ethers or fatty acid glycerides are commonly used for this reactant. Suitable materials have molecular weights between about 500 and 5000; preferably between about 1000 and 3000. The polyethers are essentially linear with terminal hydroxyl groups. The polyesters employed are prepared with excess glycol and accordingly have low acid numbers and moderate to high hydroxyl numbers. In general, the reactive hydrogen liquids have hydroxyl numbers between about 300 and about 20 and acid numbers (polyesters and fatty acid glycerides) less than about 10. The hydroxyl number is a direct measure of the density of reactive hydrogens and indicates the degree of cross-linking in the product. Generally, rigid foams are highly cross-linked and are prepared from components having hydroxyl numbers between about 180 and about 300. The flexible foams are obtained from components having hydroxyl numbers between about 20 and about 100, while semi-rigid foams are obtained from components having hydroxyl numbers between about 100 and 180.
The polyesters which can be employed in the foam formulation are obtained by the reaction of saturated alkyl or aryl dibasic acids or anhydrides with polyhydric alcohols in the manner well known to the art. Commercially available materials are prepared from adipic, sebacic, maleic, terephthalic, isophthalic acids and ethylene glycol, trimethylol ethane, trimethylol propane, etc.
The polyalkylene ethers useful as the reactive hydrogen liquid are obtained by polymerization of various alkylene oxides, commonly ethylene oxide or propylene oxide. Examples of such materials are mixed polyglycols of ethylene, propylene, polytetiamethylene glycol, polypropylene glycol, polyethylene glycol, etc.
Fatty acid glycerides can also be used as the reactive hydrogen liquid to yield a low cost foam. Commonly employed glycerides are castor oil, tall oil, soya oil, linseed oil, etc., which are usually admixed with up to equal amounts of low molecular weight polyols to increase the density of cross-linking sites. Among the low molecular weight polyols so used are triisopropanol, hexitols, ethylene glycol, trimethylol ethane, and polyhydric derivatives of alkylene diamines, e.g., Quadrol marketed by the Wyandotte Chemical Company which is N,N,N',N-tetrakis(2 hydroxypropyl) ethylene diamine.
The diisocyanates employed in the urethane foam preparation are, in general, arylene diisocyanates and include the following: 2,4-tolylene diisocyanate, 2,6- tolylene diisocyanate, 3,3-bitolylene diisocyanate, diphenylmethane, 4,4 diisocyanate, 3,3 dimethyl diphenylrnethane, 4,4'-diisocyanate, m-phenylene diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-sulfonylbis- (phenyl isocyanate), 1 chloro-2,4-phenylene diisocyanate, l,5-tetrahydronaphthylenediisocyanate, etc.
The amount of isocyanate employed in the formulation depends on the number of reactive hydrogens in the polyalkylene ether, polyester or fatty acid glyceride, which as previously mentioned is selected to obtain the desired degree of crosslinking. The amount of isocyanate employed is also determined by the nature of the gas generating agent and the density desired in the foamed product since the use of water as a gas generating agent consumes a stoichiometric amount of isocyanate.
Generally, when water is added to react with the diisocyanate, approximately 1 to about 10 equivalents of isocyanate; preferably between about 2 and about 6; are employed per equivalent of reactive hydrogen in the formulation. Substantially all the diisocyanate in excess of the equivalent amount consumed by the urethane formation is consumed in carbon dioxide formation with water.
In general, between about 1 and about 10 parts by weight of water are used per parts by weight of urethane reactants; preferably this amount is between about 2 to 7 parts per 100 parts. As previously mentioned, diisocyanate in excess of the stoichiometric amount needed for the reactive hydrogen liquid must be used with this technique to react with the water and liberate carbon dioxide; preferably the diisocyanate is also used in a slight excess than the additional amount consumed by reaction with water.
If desired, all or a portion of the water can be replaced with a latent gas generating component, such as the halogenated hydrocarbons, e.g., tn'chlorofiuormethane, trichlorotrifluoroethane, dichlorodifluoromethane, etc. Generally, these volatile liquids are used in amounts up to 25 weight percent of the urethane reactants, de pending on desired foam density and on character of ingredient as well as ambient conditions.
To stabilize the foam, various surface active agents can be used in amounts between about 0.5 and 5.0 weight percent of the reactants. Generally non-ionic surface active agents are used, however, silicone emulsifiers can also be used, particularly with the aforementioned halogenated hydrocarbon blowing agents. Examples of suitable non-ionic surface active agents are ethylene oxide condensates of vegetable oils, alcohols, phenols, organic acids and hydroxy esters. Included in such compounds are castor oil, tall oil, linseed oil condensates of ethylene oxide having 5 to 70 weight percent of oxyethylene units. Alkylphenol polyoxyethylene compounds having one or more alkyl side chains with about 5 to 20 carbons and 5 to 70 weight percent of an oxyethylene chain can be used, e.g., ethylene oxide condensate of lauryl phenol, of 2,4-dihexyl phenol, ,of heptenyl cresol, of decyl resorcinol, of decenyl xylenol, etc. Ethylene oxide condensates of fatty acids having about 10 to about 25 carbons and about 5 to 70 weight percent of ethylene oxide units are also useful, e.g., condensates with lauric, stearic, oleic, linoleic, palrnitic acids, etc. Ethylene oxide condensates of esterified polyhydric alcohols can also be used such as condensates of sorbitan monostearate, mannitan monolaurate, etc. having 5 to 70 weight percent of ethylene oxide units. The condensates at 5 to 70 weight percent ethylene oxide and fatty amines or amides with about 10 and 25 carbons can also be used such as the condensates of dodecanamide, tridecyl amine, hexadecyl amine, hetadecanamide, etc.
Tertiary amines and/ or organic tin compounds can be used as catalysts for the reaction in the manner known to those skilled in the art. Examples of various amine catalysts are: triethylenediamine, N-alkylmorpholines, e.g., N-methylmorpholine, N-ethylmorpholine, N-butylmorpholine, trialkyl amines, e.g., trimethylamine, dibutyl ethylarnine, dihexyl decylarnine, etc. Examples of suitable tin compounds are tin salts of fatty acids, e.g., stannous octoate, stannous acetate, stannous propionate, stannous stearate, stannous oleate, etc. Dialkyl tin salts can also be used, e.g., dibutyl tin dilaurate, diethyl tin oleate, diisopropyl tin acetate, dihexyl tin stearate, etc. In general, the catalyst is employed in amounts between about 1 and about 12 weight percent of the urethane reactants; preferably in amounts between about 1 and 5 weight percent.
In the practice of my invention, the ion exchange solid is dispersed in the volatile organic solvent by adding the solid to the solvent with agitation. The grit and large solid particles which settle from the suspension are discarded and, preferably, the suspension is elutriated to reject all particles coarser than microns and save for use all particles finer than 5 microns. The clarified and elutriated suspension is then ready for use in the polyurethane formulation, for acidification and/or base exchange with a quaternary organic ammonium cation prior to its use in the polyurethane formulation.
The suspension of kaolin, organophilic kaolin or organophilic montmorillonite is added, preferably with stirring, to the liquid reactive hydrogen component of the polyurethane reactant, i.e., the polyalkylene ether, polyester or fatty acid glyceride. Upon addition of the suspension, the admixture is heated under atmospheric or reduced pressures to evaporate the solvent. Generally temperatures from about 80 to about 250 C. are sufficient for this purpose. This solvent can be condensed and reused to prepare new solid suspensions. The solidreactive hydrogen liquid suspension so prepared is very stable, samples exhibiting little or no phase separation after storage for several weeks to several months.
The remainder of the polyurethane preparation follows conventional practice. The one-shot technique is preferred, wherein the blowing agent (water or halogenated hydrocarbon), catalyst, and surfactant are added to the reactive hydrogen component and the resultant single blend is subsequently admixed with the organic diisocyanate to form a reacting mass which is discharged into the mold.
My invention can also be used in the prepolymer technique wherein the diisocyanate is aged with all or a portion of the reactive hydrogen component for several minutes to several hours prior to addition of the catalyst. In this embodiment, which is preferably used when a fatty acid glyceride is the reactive hydrogen liquid, all or a portion of the reactive hydrogen component comprises the aforedescribed solid suspension of clay or organophilic clay in reactive hydrogen reactant.
The following are illustrative of polyurethane formulations of my invention.
FORMULATION 1.-LOW DENSITY RIGID A crude mixture of rosin, oleic, linoleic and stearic acids in which is suspended parts by weight of an organophilic montmorillonite per 100 parts of tall oil.
FORMULATION 2.LOW DENSITY SEMLRIGID Prepolymer: 1 Parts by weight 2,4-tolylene diisocyanate 100 Castor oil 150 Water 5 Diethyl cyclohexylamine 5 1 Prepolymer aged for 30 minutes at 75 C.
-A fatty acid glyceride having a hydroxyl number of 160 in which is stably dispersed parts by Weight of lauryl ammonium heetorite per 100 parts of castor oil.
FORMULATION 3. HIGH DENSITY RIGID Prepolymer: 1 Parts by weight 2,4-tolylene diisocyanate 36 Soya oil 113 Water 4 Diethylcyclohexylamine 3 1 Prepolymer aged for '20 minutes at C.
A fatty acid glyceritlc having a hydroxyl number of 49 in which is stably dispersed 30 parts by weight of polystyrene ammonium kaolin (average molecular weight l000; weight percent polymer on clay 2.5) per parts of soya 011.
To illustrate the results obtainable by my invention and to contrast such results with prior art suggested techniques, the following examples are presented:
EXAMPLE 1 Samples of a commercially obtainable montmorillonite, Wyoming bentonite, and kaolinite were stirred into methanol to form suspensions of about 100 grams of clay per liter of methanol. Grit and large particles of clay settled from the suspension and removed. The degritted clay suspensions were thereafter divided into several portions and one portion of each clay suspension was used directly in the urethane foam preparation.
The second portion of each clay suspension was passed upwardly through an eleutriation zone to recover the finest portion having a particle size distribution between 0.01 and about 5 microns. The eleutriated fraction was again divided and one portion thereof was acidified by the addition of 10 milliliters of 38 percent hydrochloric acid per 100 grams of clay. The acidified clay was filtered from suspension and washed several times with 250 mililiters of methanol per 100 grams of clay, filtering the clay after each wash step. Each of the final suspensions of about 25 weight percent clay in methanol was thereafter divided into two fractions and an amino polyol, dioxyethylene propanol amine, was added to one fraction of each clay suspension in a suificient quantity to achieve neutralization of the hydrogen clay. The resultant organo montmorillonite contained about 7.5 weight percent unextractable organic matter and the resultant organokaolinite contained about 0.4 weight percent unextracta'ble organic matter.
The aforedescribed methanol suspensions of clays, fractionated clays, acidified (hydrogen) clays and organoclays were then aded to separate portions of Niax LHT- 67, a polyoxypropylene triol, having a molecular weight of 2500. This product is identified in Union Carbide Chemicals Company Technical Information Bulletin, F-40378A of April 1959, as comprising a straight polyoxypropylene adduct with hexane triol and an average hydroxyl number of 67. The methanol was removed by evaporation. To each grams of the resultant polyolclay suspensions was added:
Grams Dibutyl tin dilaurate 1.5 Silicone L-52O 1.5 Water (in amounts indicated below).
A polysiloxane-polyoxyalkylene block copolymer prepared in accordance with the disclosure in US. Patent Number 2,834,748.
The admixtures were stirred thoroughly in a high speed mixer and thereafter 49 grams of tolylene diisocyanate was added, the mixtures were stirred for an additional 20 seconds, and then poured into molds. After five minutes at room temperature the resultant foams were placed in an oven at 150 F. for four hours, removed, visually inspected and tested. The following table summarizes the results.
sin, a hydroxyl A portion of the aqueous ried to obtain a powtions of the hy- The following table igated and re ned by passing an aqueous in through a column of an To other por tions of hydrogen montmorilsimilar manner were added various kaolin and to por the hydrogen kaolin was obtai ammonium charged ion exchange cation re charged anion exchange resin and finally a hydrogen charged cation exchange resin.
suspension was thereafter spray d dered hydrogen clay solid.
lonite obtained in a organic amines in amounts sufficient to neutralize the hydrogen clays. The resultant organoclay suspensions were then spray dried to obtain a powdered solid which was added to the polyol system.
describes the types of organoclays invest Table 1 suspension of the degritted kaol drogen sults so obtained.
the
Table 2 t ine mple was ob- EXAMPLE 2 illustrates the results ob id directly to the polyol d by the prior art. olyol Were 3 milliliters of water, 1.5 .5 grams of dibutyl tin The polyol suspension was thereigh speed stirrer and, milled in a ball mill or heated prior to The amounts of yed are set forth ich summarizes the results.
loyed in this exa lin in 95 volumes of water, and
- Sample No.
0 H 0 0 I mm n m w a w a m am m 8 mwo p R e m n e n rawflm afi ec mD mm.m0 2 NF flue 74289499 167 7 005783117 e 22223 11 211 Q rw ats 9.51 T w m 0406000 250 6 80668853 6 M 23 5 5112 7 LL L 40 5 5 0 0 om0 p .Q-v 2222222 222 1 29-222219- m a P fi m F 89064 86 32 7 1903 04 0 7777398 31 9 9630 528 w 22222.12 221 2 29.33 3222 m. w S m 50500 L 3333453 4 55 3333 333341 55 mm t. we
6666666 666 6666 8466666 S 7 7 7 7 7 7 7 7 7 7 7 7 oak- 7 7 710 m 11111 1 11 1111 11111 a r G .e Rm .5 D. n "0m NH e m .m .n ne m em m m v. will m a m0 8 .g 1 a h 1 "n C n 1k .1 00 i o m mmm fi 10 m .a D m mmp uh n da. m o 0 en u re S E D .a e t 0 m .0 D on u o a 0 1 d m 3 .m .1 m W 1 1 t da v.0 h mm m enmmm T fifi H t fiwum b m ii 0 i o w 0 0 a $01 3 .11 3.10m 1 C0 in B 0 AA DFA P n n The following example by adding a powdered clay sol mixed thoroughly with a h where indicated, addition of the tolylene diisocyanate.
olyol and diisocyanate emplo g table wh The degritted kaolin emp tained by suspending kao of a urethane as heretofore practice Alsoadded to the p "grams of a silicon surfactant and 1 dilaurate catalyst.
after followin X 8 F t O O r o H I o n m p mm S a 1 1 a k .m w .mm M f. 2 W. m 0 ma i. 8 e mp R m mrmunh t m J -l u m n 1 m wm w T 1 f r M nmmerw P M PH m a 2 1. a 9.9.2 1. 1.1.9.2 21.211212 mw wm T m m w 0 68 A. 0029 89068 282427561 1 6 7 0 6 &7 3 00 8 Z o n r. 6p P T m 1 6390 86051.13 0 0 m am an anew 21.2.. 2510 495 F W Z Z2 333332333 .1 S s Db l 3 3 9 3O 00 0 0000 0000 0 0 000000000 15 55 5555 5 5 555555555 Wm H M M mull 1111 1 1 111111111 aw PG 1 9 99 9999 999999999 Dm o 5 5 55 2 3 65 365365365 05 00 500 a na w on awe 361361361 r G n n n u L. m u "H t n m r .r i 0 0 .0 n m O S m m .m t m m o t .m k a m m 3 w a a. m n m .m v. .m m ns .w a n m .0 0 W 0 a m u .m m e i .1. m a m ammo r r w n u mt e n m :m. .m S .9 8 D pt e D H 03 .n t .0 .0 n 0 e 0e .a n .C .i D C mi. 0 0 2m m m he. wm. .m .m m "w u a. mfl lr .m .n m. v .mw mm I y .m e h l e .h. nu mr 1. de a. 0 M0 mme fl m o ohm. 0 0.0 m0 om 0m d d .1 t o .xod d d n 0 d d n CYiV W0 .0 d O mmnmm .1m "9 ml V. u "0 n "0 I M CD1 P LAPD T B H P n P n n U n 0 u U 0 n n m n m m m m u h u "n I m u u n o t. u n N n. I a. n s 5 6 7 8 9 0 1 2 3 a 0 1 o 1 2 22 29- 3 333% 3 44 5 A comparison of the tensile and tear strengths of samples 1 through 6 (Table 1) to the properties of the unfilled foam and to the properties of samples 22 through 25 (Table 2) will show that my preparation of urethane foam results in:
(1) Clay filled foams having tensile and tear strengths greater than unfilled foams;
(2) Clay filled foams which can be extended to a lower bulk density than unfilled foams without impairing the tensile and tear strength of the foam; and
(3) Clay filled foams which have greater tensile and tear strengths than obtained by prior art suggested techniques of adding the clay filler.
A comparison of results from samples 24 and 25 indicates that attempts to mill the clay into the polyol did not improve the foam properties. Samples 7 through 10 illustrate the results obtainable with organokaolin clays, which substantially duplicate the results of the inorganic kaolin filled clays, samples 1 through 6.
Samples 11 through 14 illustrate the failure of urethane foams which occurs when inorganic montmorillonite clays are used as fillers. I have found that this behavior can be avoided by 'base exchanging an organic amine onto the clay in an amount greater than about one weight percent and the samples 14 through 21 demonstrate results obtainable with such organophilic montmorillonites. From this data it can be seen that foams of reduced density can be obtained with substantially no reduction in tensile strength compared to the unfilled foam.
The remaining data in Table 2 illustrates that foams of improved tensile and tear strengths can not be obtained from clays or organoclays by adding the dry clay powder directly to the polyol used in the urethane formulation.
The preceding data are presented solely to illustrate my preparation of urethane foams and are not to be construed as unduly limiting of my invention which is defined by the following claimed sequence of method steps and equivalents thereof.
I claim:
1. In the preparation of cellular polyurethanes wherein a reactive hydrogen liquid having a molecular weight between about 500 and 3,000, a hydroxyl number between about and about 300 and selected from the class consisting of polyalkylene ethers, fatty acid glycerides, polyesters of dibasic acids and dihydric alcohols having acid numbers less than about 10, and mixtures thereof, is reacted with an excess of an arylene diisocyauate in the presence of a blowing agent, a catalyst and a surface active agent; the improved method of incorporating an aluminum silicate solid filler within said cellular polyurethane which comprises forming a suspension of said aluminum silicate solid in a volatile organic liquid having a boiling point lower than said reactive hydrogen liquid, admixing said suspension with said reactive hydrogen liquid, removing said volatile organic liquid by evaporation and thereafter admixing and reacting said reactive hydrogen liquid with said arylene diisocyanate.
2. The method of claim 1 wherein said aluminum silicate solid is a clay selected from the class consisting of kaolin, orgnophilic kaolin and organophilic montmorillonitc.
3. The method of claim 1 wherein the amount of said clay comprises between about 2 and about 20 weight percent of the total weight of the organic polyurethane reactants.
4. The method of claim 2 wherein said aluminum silicate is an organophilic kaolin and is prepared by (1) suspending kaolin in an acidification medium comprising a mixture of hydrochloric acid in methanol to convert the kaolin to hydrogen kaolin, (2) filtering the resultant hydrogen kaolin from the acidification medium, (3) suspension of the filtered hydrogen kaolin solid in said volatile organic liquid,'and (4) addition of an organic amine to the suspension of said hydrogen kaolin in an amount sufficient to neutralize said hydrogen kaolin and form said organophilic kaolin having between about 0.05 and 10 weight percent of chemically bonded organic matter.
5. The method of claim 2 wherein'said aluminum silicate is an organomontmorillonite and is prepared by (1) suspending montmorillonite in an acidification medium comprising a mixture of hydrochloric acid in methanol to convert said montmorillonite to hydrogen montmorillonite, (2) filtering said hydrogen montmorillonite'from said acidification medium, (3) suspension of the filtered hydrogen montmorilionite solid in said volatile organic liquid, and (4) addition of an organic amine to the suspension of said hydrogen montmorillonite in an amount suflicient to neutralize said hydrogen montmorillonite and form said organophilic montmorillonite having 'between about 2 and about weight percent of chemically bonded organic matter.
References Cited by the Examiner UNITED STATES PATENTS 3,015,634 2/1962 Ferrigno 2602.5 3,024,209 3/1962 Ferrigno 2602.5 3,029,209 4/1962 Ferrigno 2602.5
FOREIGN PATENTS 158,769 9/1962 Australia.
LEON J. BERCOVITZ, Primary Examiner.
Claims (1)
1. IN THE PREPARATION OF CELLULAR POLYURETHANES WHEREIN A REACTIVE HYDROGEN LIQUID HAVING A MOLECULAR WEIGHT BETWEEN ABOUT 500 AND 3,000, A HYDROXYL NUMBER BETWEEN ABOUT 20 AND ABOUT 300 AND SELECTED FORM THE CLASS CONSISTING OF POLYALKYLENE ETHERS, FATTY ACID GLYCERIDES, POLYESTERS OF DIBASIC ACIDS AND DIHYDRIC ALCOHOLS HAVING ACID NUMBERS LESS THAN ABOUT 10, AND MIXTURES THEREOF, IS REACTED WITH AN EXCESS OF AN ARYLENE DIISOCYANATE IN THE PRESENCE OF A BLOWING AGENT, A CATALYST AND A SURFACE ACTIVE AGENT; THE IMPROVED METHOD OF INCORPORATING AN ALUMINUM SILICATE SOLID FILLER WITHIN SAID CELLULAR POLYURETHANE WHICH COMPRISES FORMING A SUSPENSION OF SAID ALUMINUM SILICATE SOLID IN A VOLATILE ORGANIC LIQUID HAVING A BOILING POINT LOWER THAN SAID REACTIVE HYDROGEN LIQUID, ADMIXING SAID SUSPENSION WITH SAID REACTIVE HYDROGEN LIQUID, REMOVING SAID VOLATILE ORGANIC LIQUID BY EVAPORATION AND THEREAFTER ADMIXING AND REACTING SAID REACTIVE HYDROGEN LIQUID WITH SAID ARYLENE DIISOCYANATE.
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US5447963A (en) * | 1994-07-14 | 1995-09-05 | Pmc, Inc. | Method for reducing volatile emissions generated during the preparation of foams and fabrication of foam products |
US5482980A (en) * | 1994-07-14 | 1996-01-09 | Pmc, Inc. | Methods for preparing flexible, open-celled, polyester and polyether urethane foams and foams prepared thereby |
US5717000A (en) * | 1996-02-23 | 1998-02-10 | The Dow Chemical Company | Despersions of delaminated particles in polymer foams |
US5952093A (en) * | 1997-02-20 | 1999-09-14 | The Dow Chemical Company | Polymer composite comprising a inorganic layered material and a polymer matrix and a method for its preparation |
US20100196506A1 (en) * | 2009-01-30 | 2010-08-05 | Indulis Gruzins | Preparation of a pyrithione salt dispersion usable in urethane applications |
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